KR20090104078A - Polymer mixture comprising a comb copolymer - Google Patents

Abstract

The invention relates to a polymer mixture consisting of at least one comb copolymer (I) containing blocks of special structural units and at least one copolymer (Il) comprising polymerised, optionally substituted styrene and maleic anhydride units, the carboxyl groups of which are at least partly present as alkaline metal salts, earth alkaline metal salts or ammonium salts. The invention also relates to the use of said polymer mixtures as wetting agents and dispersants.

Description

Polymer mixture comprising a comb copolymer

The present invention is polymerized and optionally substituted, wherein at least one comb-copolymer (I) and carboxyl groups containing blocks consisting of specific structural units according to claim 1 are present at least partially as alkali metal salts, alkaline earth metal salts or ammonium salts. It also relates to polymer mixtures comprising at least one copolymer (II) comprising styrene and maleic anhydride units, and also to the use of these polymer mixtures as wetting and dispersing agents.

It is known that many comb copolymers can be used as wetting and dispersing agents for solids, especially pigments. Accordingly, comb copolymers obtained by converting styrene / maleic anhydride copolymer (SMA resin) as the main chain using polyalkylene oxide amine and polyalkylene glycol as side chains are already known from the prior art.

For example, in addition to imide structures, suitably prepared comb copolymers having amide and ester linkages of side and back chains are described in US Pat. No. 6,310,143. Such comb copolymers do not guarantee sufficiently high viscosity reductions as dispersants and wetting agents for some uses and, as a result, do not formulate suitably flowable pigment pastes or produce any pigment pastes having a desired high pigment content. Can not.

Thus, on the basis of this prior art, solid pastes having very desirable fluidity, despite high solids content, using comb copolymers based on known styrene-maleic anhydride copolymers as wetting agents and dispersing agents, Preferably it is necessary to modify the pigment paste so that it can be obtained.

The purpose is

(a) at least one block of copolymer comprising structural units of formulas (I) to (IV) wherein X ₁ is NH and / or

(b) one or more blocks of copolymers comprising structural units of formulas (I), (II) and (IV) wherein X ₁ is O and / or

(c) at least one block of copolymer comprising structural units of formulas (I) to (IV) wherein X ₁ is NH or O and / or

(d) at least one block comprising a structural unit of formula (I) and a polymerized unit of at least one ethylenically unsaturated monomer different from the structural units of formulas (II) to (IV), wherein block (d) is merely a block (a) to at least one comb copolymer (I) in combination with one of (c) to form a block copolymer and

Polymer according to the invention comprising at least one copolymer (II) based on the structural unit of formula (I) and the structural unit of formula (IV), in which the carboxyl group is at least partly in the form of an alkaline earth metal, ammonium or an alkali metal salt This is accomplished by making the mixture available.

In Chemical Formulas I to IV,

는 쇄 결합을 나타내고,

Represents a chain bond,

R is H, halogen, preferably chlorine, nitro group, alkyl group of 1 to 15 carbon atoms or aryl group of 6 to 18 carbon atoms,

R ₁ is an alkylene group having 1 to 24 carbon atoms or a substituted or unsubstituted arylene group having 6 to 18 carbon atoms,

R ₂ is H and / or an alkyl group,

z is an integer from 3 to 70,

X ₁ is NH and / or O,

R ₃ is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted cycloalkyl group having 4 to 10 carbon atoms,

The free carboxyl group of the structural unit of formula IV may be in the form of an alkali metal, alkaline earth metal or ammonium salt.

Preferably, in the structural units of formulas (I) to (IV),

R is H,

R ₁ is an alkylene group having 1 to 6 carbon atoms,

R ₂ is H and / or CH ₃ , wherein the molar ratio of ethylene oxide units to propylene oxide units in the structural units of formula II and the structural units of formula III is from 0: 100 to 100: 0,

R ₃ is an alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 carbon atoms,

X ₁ is NH and / or O,

Z is an integer from 5 to 60.

In the structural unit of formula (I) to (IV),

R is H,

R ₁ is an ethylene, propylene and / or isopropylene moiety,

R ₂ is H or CH ₃ residue, wherein the molar ratio of ethylene oxide units to propylene oxide units is from 70:30 to 30:70,

R ₃ is CH ₃ or C ₂ H ₉ residues,

z is an integer from 27 to 50,

Particular preference is given when R ₁ is NH and / or O.

The polymer mixture according to the invention preferably consists of at least one copolymer (I) and at least one copolymer (II). The weight ratio of comb copolymer (I) to copolymer (II) preferably falls in the range of 50:50 to 95: 5.

The comb copolymer (I), for example, comprises one optionally substituted styrene / maleic anhydride copolymer

(a1) preferably using at least one polyalkylene oxide monoamine having a primary amino end group at a reaction temperature of at least 150 ° C., optionally further converted at a reaction temperature of less than 100 ° C.,

(a2) is preferably converted using a mixture of one or more polyalkylene oxide monoamines with primary amino terminal groups and one or more monohydroxy-terminated polyalkylene oxides at reaction temperatures of at least 150 ° C., where Thus, further conversion at a reaction temperature of less than 100 ° C, or

(a3) preferably converted using one or more monohydroxy-terminated polyalkylene oxides in the presence of conventional esterification catalysts such as sulfonic acid,

Maleic acid in which the A block is optionally substituted with styrene units and at least one copolymerized ethylenically unsaturated monomer selected from the group comprising (meth) acrylates and dialkyl maleateates, and the B block is copolymerized with optionally substituted styrene units One or more copolymers having an AB block copolymer structure comprising anhydride units can be obtained by converting using (a1), (a2) or (a3).

According to the invention, at least one comb copolymer (I) is mixed with a second mixture component, wherein copolymer (II) is at least one SMA resin comprising optionally substituted styrene units and copolymerized maleic anhydride units From the hydrolysis and chloride. In the case of copolymer (II), the free carboxyl groups are at least partially present in the form of alkaline earth metal, ammonium or alkali metal salts.

The SMA resin used to prepare the comb copolymer (I) or copolymer (II) is an optionally substituted styrene maleic anhydride copolymer, where styrene is an alkyl group having 1 to 15 carbon atoms, preferably methyl, carbon Optionally substituted with 6 to 18 aryl groups, halogens, preferably chlorine or one or more nitro groups.

Thus, according to the present invention, the term "S" in the SMA resin is understood to denote both substituted styrene and unsubstituted styrene.

SMA resins can have a statistical, alternating, gradient or block structure. These can be prepared by radical initiated polymerization methods, for example using azo- or peroxide initiators. To set the desired molecular weight, chain transfer agents such as thiols, secondary alcohols or alkyl halides such as carbon tetrachloride can be added during the polymerization. Further suitable processes for the preparation of SMA resins are controlled radical polymerization methods, for example:

When certain chain transfer agents are used, they are also referred to as MADIX and addition fragmentation chain transfer agents and are described, for example, in Polym. Int. 2000, 49, 993; Aust. J. Chem. 2005, 58, 379; J. Polym.Sci.Part A: Polym. Chem. 2005, 43, 5347; US 6 291 620, WO 98/01478, WO 98/58974 and WO 99131144), the reversibility referred to herein only as RAFT. Reversible addition fragmentation chain transfer process (RAFT) or

Controlled polymerization using nitroxyl compounds (NMP) as polymerization regulators, as described, for example, in Chem. Rev. 2001, 101, 3661.

The C-RAFT process described in US Pat. No. 6,291,620 is particularly preferred as a polymerization technique. Corresponding described descriptions apply as part of the present specification.

The optionally substituted styrene maleic anhydride molar ratio of the SMA resin preferably belongs to 1: 1 to 8: 1. An optionally substituted molar ratio of styrene maleic anhydride 1: 1 to 2: 1 is particularly preferred for obtaining high density side chains. The number average molecular weight of the SMA resin used is preferably 1,000 to 20,000 g / mol (measured by GPC).

The C ₁ -C ₄ monoalcohols disclosed polyethers formed from ethylene oxide and propylene oxide units and comprising primary amino groups as terminal groups are preferably polyalkyls for the preparation of comb polymers (I) used according to the invention. Used as lene oxide monoamine. The weight ratio of ethylene oxide to propylene oxide units should preferably be from 0: 100 to 100: 0, particularly preferably from 30:70 to 70:30. The number average molecular weight of the polyalkylene oxides used is preferably 500 to 3000 g / mol (measured via amine titer or ¹ H-NMR spectroscopy).

The monohydroxy-terminated polyethers used in the conversion (a2) or (a3) are preferably polyalkylene oxides. The weight ratio of ethylene oxide to propylene oxide units of the monohydroxy-terminated polyether is preferably 0: 100 to 100: 0, particularly preferably 30:70 to 70:30. The number average molecular weight is preferably 200 to 3000 g / mol (measured by ¹ H-NMR spectroscopy).

A block is formed from optionally substituted styrene units and one or more copolymerized ethylenically unsaturated monomers selected from the group comprising (meth) acrylates and dialkyl maleateates, wherein the B blocks are formed of the structural components of formulas (I), (II) and (IV). AB block copolymers formed from combinations or combinations of structural components of formulas (I) to (IV) wherein X ₁ is O and / or NH can also be used as comb copolymers (I) according to the invention.

Examples of aryl or alkyl (meth) acrylates are alkyl (meth) acrylates of straight, branched or cycloaliphatic alcohols having 1 to 22 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, n -Butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) Acrylates, cyclohexyl (meth) acrylates, isobornyl (meth) acrylates and tert-butyl (meth) acrylates; Aryl (meth) acrylates such as benzyl methacrylate or phenyl acrylate, where the aryl moieties may each be unsubstituted or substituted up to four times, for example 4-nitrophenyl methacrylate.

The weight ratio of A block to B block is preferably in the range of 95: 5 to 5:95, particularly preferably in the range of 90:10 to 10:90.

The maleic acid semi-ester (structural component II) is preferably converted, for example, of maleic anhydride to monohydroxy-terminated polyethers, preferably monohydroxy-terminated polyalkylene oxides as described above. Product.

These can be used for polymerization by themselves and / or can be prepared in situ after polymerization by reacting polymerizable maleic anhydride with the polyethers described above and / or by conversion of the SMA resin to the polyethers described above.

In a preferred arrangement, the comb copolymer (I) used according to the invention can preferably be obtained by first dissolving one or more SMA resins in a suitable solvent. To this end, a mixture of one or more polyalkylene oxide monoamines or one or more polyalkylene oxide side monoamines and one or more of the aforementioned monohydroxy-terminated polyethers or only one or more monohydroxy-terminated polyethers is added. Converting to a degree such that at least 50% of the anhydride structures of the copolymers forming the respective main chains are preferably converted at a temperature of preferably 20 to 200 ° C, particularly preferably 30 to 170 ° C, particularly preferably 150 ° C or more. Let's do it. In this case, the primary amino group is reacted with the anhydride structure of the copolymer to form amides and / or imides, where amide formation is encouraged at low reaction temperatures and imide formation is encouraged at increasing reaction temperatures, or The hydroxyl group is reacted with an anhydride structure to form a semi-ester. Almost only amide bonds are formed at reaction temperatures of 20-50 ° C., while imide formation is supported at temperatures above 140 ° C. Since water is released in the case of imide formation, the anhydride structure of the further copolymer can be converted to the carboxylic acid functional group. In each of these conversions, the solvent initially added may be distilled again to remove water produced by imide formation, if desired, by azeotropic distillation.

The use of a solvent during the conversion of the copolymer with the amino component and / or the monohydroxy-terminated component demonstrates that all anhydride groups of the copolymer can react in substantially the same manner as the initial conversion. More homogeneous preparations are obtained as a result of this.

According to the present invention, comb copolymers or comb block copolymers refer to polymers, copolymers or block copolymers as base polymers or polymer backbones, which are linked with linear polymer side chains via ester, amide and / or imide bonds. It is understood that.

The second mixture component of the polymer mixture according to the invention is an SMA resin. This SMA resin is preferably of statistical, alternating, gradient or block structure, wherein the molar ratio of optionally substituted styrene to maleic anhydride is from 1: 1 to 8: 1, preferably from 1: 1 to 2: 1. The anhydride groups of the SMA resin are preferably 100% hydrolyzed and the free carboxyl groups are preferably 100% chlorinated. The above-mentioned polyalkylene oxide monoamines and optionally substituted monoamine compounds terminated with primary amino groups, for example N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-di Butylethanolamine, methyl diethanolamine, ethyl diethanolamine or triethanolamine are used for the chloride.

Chloride can also be accomplished by the addition of suitable alkali or alkaline earth metal salts.

The polymer mixtures according to the invention are suitable as wetting and dispersing agents for many aqueous use purposes known from the prior art. They thus prepare or process paints, printing inks, inkjet processes, for example ink for inkjet printers, coatings, leather and textile dyes, pastes, pigment concentrates, ceramics, cosmetic preparations, preferably solids, For example, it can always be used when pigments and / or fillers are present. For example, the polymer mixtures according to the invention can be used to produce industrial paints, wood and furniture varnishes, automotive paints, marine paints, anticorrosive paints, cans and coil coatings, artists and household paints, optionally optionally Auxiliaries of, for example, known binders and / or solvents, pigments and optionally fillers are added to the polymer mixture according to the invention.

Examples of common binders are resins based on polyurethanes, cellulose nitrates, cellulose acetobutyrates, alkyds, melamines, polyesters, chlorinated rubbers, epoxides and acrylates.

The polymer mixtures according to the invention are also suitable as wetting and dispersing agents for producing aqueous coatings, for example cathodic or anode electrocoatings for automotive bodies. Further use examples as dispersants are plasters, silicate paints, dispersion paints, aqueous paints based on alkyds which are dilutable with water, alkyd emulsions, hybrid systems, two-component systems, polyurethane and acrylate dispersions.

The polymer mixtures according to the invention are also particularly suitable for producing solid concentrates, preferably pigment concentrates. To this end, they are present in a supporting medium such as inorganic solvents, softeners and / or water and are added to the dispersible solid with stirring. In addition, these concentrates may contain binders and / or other auxiliary substances. However, it is also advantageously possible to produce stable binder free pigment concentrates using the polymer mixtures according to the invention. The polymer mixtures according to the invention can be used to equally prepare flowable pigment concentrates from pigment press cakes. In this case, the polymer mixture according to the invention is added to a press cake which may contain water and the mixture thus obtained is dispersed. These solid concentrates, preferably pigment concentrates, can then be treated in different substrates such as alkyd resins, polyester resins, acrylate resins, polyurethane resins or epoxy resins. Directly dispersed solvent-free pigments in the polymer mixtures according to the invention are particularly suitable for coloring thermoplastic and thermoset plastic formulations.

The polymer mixtures according to the invention can also advantageously be used to prepare inks for "non-impact" printing processes, for example thermal transfer inkjet and bubble-jet processes. These inks can be, for example, aqueous ink formulations.

The polymer mixtures according to the invention can also be used to prepare cosmetic preparations such as foundations, powders, lipsticks, hair dyes, creams, nail polishes and sunscreen preparations. They may be present in conventional formulations, for example in the form of W / O or O / W emulsions, solutions, gels, creams, lotions or sprays. In this case, the polymer mixtures according to the invention can already be used as dispersants in the dispersions used to prepare these preparations.

The invention furthermore relates to the use of the polymer mixtures according to the invention as wetting and dispersing agents. These wetting agents and dispersants are preferably used for the above-mentioned use purposes.

A further purpose of use is also the preparation of colored coatings on the substrate, applying the pigment paint to the substrate and burning, curing or crosslinking the applied pigment paint.

For the purpose of using the polymer mixtures according to the invention, they can optionally be used with conventional binders according to the prior art.

The use according to the invention is, inter alia, the production of dispersible solids in the form of powder particles and / or fiber particles, in particular the production of dispersible pigments, which particles can be coated with the polymer mixtures according to the invention. Such coatings of organic or inorganic solids are arranged in a known manner, for example as in EP-A 0 270 126. In such cases, the solvent or emulsifier may be removed or remain in the mixture to form a paste. Such pastes are commonly used industrial products which may optionally contain binders as well as additional auxiliary substances and additives.

In particular, in the case of pigments, the polymer surfaces according to the invention can be added during the synthesis of the pigments or after the synthesis, ie they can be added to the pigment suspension or during or after the pigment finish to modify, ie coat the pigment surface.

Pigments pretreated in this way are distinguished by their high color intensity and their ability to work more easily than pigments which are not surface treated.

The polymer mixtures according to the invention comprise a number of pigments, for example mono-, di-, tri- and polyazo pigments, oxazines, dioxazines, thiazine pigments, diketo-pyrrolopyrroles, phthalocyanines, ultramarines and Wetting agents and dispersants for other metal complex pigments, indigo pigments, diphenylmethane, triarylmethane, xanthene, acridine, quinacridone, methine pigments, anthraquinones, pyrantrones, perylenes and other polycyclic carbonyl pigments Suitable as. Further examples of dispersible organic pigments according to the invention are described in the paper (W. Herbst, K. Hunger "Industrial Organic Pigments", 1997 (publisher: Wiley-VCH, ISBN: 3-527-28836-8) Turns out. Examples of dispersible inorganic pigments according to the invention include carbon black, graphite, zinc, titanium dioxide, zinc oxide, zinc sulfide, zinc phosphate, barium sulfate, lithopone, iron oxide, ultramarine, manganese phosphate, cobalt aluminate, cobalt stannate Mixed metals based on cobalt, antimony zinc oxide, antimony sulfide, chromium oxide, zinc chromate, nickel, bismuth, vanadium, molybdenum, cadmium, titanium, zinc, manganese, cobalt, iron, chromium, antimony, magnesium, aluminum Pigments based on oxides such as nickel-titanium yellow, bismuth-vanadate molybdate yellow or chromium titanium yellow. Further examples are incorporated in the paper (G. Buxbaum "Industrial Inorganic Pigments", 1998 (publisher: Wiley-VCH, ISBN: 3-527-28878-3)). Inorganic pigments may also be known as pearlescent pigments, fluorescent and phosphorescent luminescent pigments, as well as metal effect pigments consisting of aluminum, zinc, copper or brass, magnetic pigments based on pure iron, iron oxides and chromium oxides or mixed oxides. . Nanoscale organic or inorganic solids having a particle size of less than 100 nm, for example, particles of particular carbon black form or of metals or semimetal oxides or hydroxides, as well as particles of mixed metals and / or semimetal oxides or hydroxides It can also disperse | distribute with the polymer mixture which follows. Oxides suitable for this are oxides and / or oxide hydroxides of aluminum, silicon, zinc or titanium which can be used for the preparation of such very fine particle solids. The preparation of these oxides or hydroxides or oxide-hydroxide particles can be carried out using a variety of methods, for example, ion exchange methods, plasma processes, sol-gel processes, precipitation, crushing (e.g. polishing) or flame hydrolysis and the like. have. These nanoscale solids may also be called so-called hybrid particles, which are formed from inorganic cores and organic shells or vice versa.

According to the invention, dispersible powders or fibrous fillers are in particular aluminum oxide, aluminum hydroxide, silicon dioxide, diatomaceous earth, silica, quartz, silica gel, talc, kaolin, mica, pearlite, feldspar, slate powder, calcium sulfate, barium sulfate, Ones formed from calcium carbonate, calcite, dolomite, powder or fibrous particles of glass or carbon. Further examples of dispersible pigments or fillers are also found in EP-A 0 270 126. The matting agent, for example silicic acid, can also be well dispersed and stabilized using the polymer mixture according to the invention.

The present invention therefore furthermore relates to paints and pastes containing at least one polymer mixture and at least one pigment, water and optionally an organic substrate and, optionally, a binder and conventional auxiliary materials according to the invention.

The invention therefore further relates to the aforementioned pigments coated with one or more polymer mixtures according to the invention.

Example:

matrix( parent ) Preparation of Compound

a) polyether MSA half-ester

375 g of Pluriol A 750 E, 42 g of polyglycol B01 / 20, 55 g of maleic anhydride are reacted at 135 ° C. for 3 hours in the presence of 2 g of dodecylbenzol sulfonic acid.

b) preparation of comb-copolymer (I)

10.5 g of Pluriol P 600, 3.9 g of 2,4-diphenyl-4-methyl-1-pentene are heated to 160 ° C. Subsequently, 8.7 g styrene, 4.2 g dibutyl maleate, 8.7 g benzyl methyl acrylate and 0.2 g Trigonox C are added over 2 hours. After 1 hour of subsequent reaction time, the temperature is reduced to 135 ° C. and 170 g of polyether-MSA semi-ester mixture obtained according to (a) is added. 34 g of styrene and 1.7 g of Trigonox C are then added to the dose over 1 hour. After 4 hours of subsequent reaction time, the reaction mixture is cooled to room temperature.

c) preparation of comb copolymer (2)

20 g of SMA 2000 synthetic resin dissolved in 60 g of butyl acetate is reacted with 116 g of Jeffamin M 2070 at 160 ° C. for 4 hours. Butyl acetate is distilled off during this time.

Wetting and dispersing agents (1) Example Manufacturing

100 g comb copolymer (1) is emulsified in 100 g of water and adjusted to pH 9 using N, N-diethylaminoethanol. The mixture is then heated to 95 ° C. for 1 hour and adjusted to 40% by weight solids.

Preparation of Wetting Agent and Dispersant (2) (mixture of the Invention)

5 g of SMA 2000 synthetic resin and 0.1 g of p-toluol sulfonic acid are emulsified with 100 g of water and reacted at 95 ° C. for 8 hours. Next, 100 g comb copolymer (1) is added and adjusted to pH 9 using N, N-diethylaminoethanol. Water content is added to adjust the solids content 40% by weight.

Wetting and dispersing agents (3) Example Manufacturing

100 g of comb copolymer 2 is dissolved in 150 g of water.

Preparation of Wetting Agent and Dispersant 4 (mixture of the Invention)

5 g of SMA 2000 synthetic resin and 0.1 g of p-toluol sulfonic acid are emulsified with 100 g of water and reacted at 95 ° C. for 8 hours. 56 g comb copolymer (2) is then added and mixed with 18 g of Jeffamine M 2070 for chloride. Water content is added to adjust the solids content 40% by weight.

Pluriol A 750 E: polyethylene glycol monomethyl ether, hydroxyl value 75 g KOH / g, manufacturer: BASF

Polyglycol B01 / 20: polypropylene glycol monobutyl ether, hydroxyl number 80 g KOH / g, manufacturer: Clariant

Pluriol P 600: Polypropylene glycol, hydroxyl value 195 g KOH / g, BASF

Trigonox C: tert-butyl peroxobenzoate, manufactured by Akzo Nobel

SMA 2000 Synthetic Resin: Styrene-maleic anhydride copolymer manufactured by Cray Valley

Jeffamine M 2070: amine terminated EO / PO polyether, manufactured by Huntsman

apply Example :

I.

Pigment concentration weight% Water Wetting Agents and Dispersants (1) to (4) BYK®-017 Hostaperm Red Violet ER02 Water 27.00 22.50 0.5 30.00 20.00 100.00

Dispersion: 40 minutes, 40 ° C. and 10000 rpm, Dispermat CV

II.

Paint applied weight% Pigment concentrate base coats according to I Silken's Autowave MM 20.00 80.00 100.00

Homogenization: shake for 5 minutes

BYK ^® -017: antifoaming agent, manufactured by Byk Chemie GmbH

Base coat Silken's autowave MM: Unpainted car paint base paint, water-based acrylate dispersion, manufacturer: Akzo Nobel

result:

Wetting and dispersing agents Pigment concentration Paint applied bubble Viscosity Transparency Pinholing Glossiness R20 / R60 One In a little Liquid limit 2 none 24/63 2 none liquidity 2 none 26/64 3 In a little Liquid limit 3 none 20/53 4 none liquidity 3 none 26/70

Rating scale:

1: good

2: satisfied

3: dissatisfaction

Glossiness was measured using a "cloudy-gloss" measuring device from Byk Gardner. Transparency or pinholes were evaluated visually. In this case, scales of 1 to 5 were used (1 = transparent; 5 = not transparent).

Claims (15)

(a) at least one block of copolymer comprising structural units of formulas (I) to (IV) wherein X ₁ is NH and / or (b) one or more blocks of copolymers comprising structural units of formulas (I), (II) and (IV) wherein X ₁ is O and / or (c) at least one block of copolymer comprising structural units of formulas (I) to (IV) wherein X ₁ is NH or O and / or (d) at least one block of copolymer comprising a structural unit of formula (I) and a polymerized unit of at least one ethylenically unsaturated monomer different from the structural units of formulas (II) to (IV), wherein block (d) is merely a block ( one or more comb copolymers (I) in combination with one of a) to (c) to form a block copolymer, and A polymer mixture comprising at least one copolymer (II) based on structural units of formula (I) and structural units of formula (IV), wherein the carboxyl group is at least partially in the form of an alkaline earth metal, ammonium or an alkali metal salt. Formula I

Formula II

Formula III

Formula IV

In Chemical Formulas I to IV,

Represents a chain bond, R is H, halogen, preferably chlorine, nitro group, alkyl group of 1 to 15 carbon atoms or aryl group of 6 to 18 carbon atoms, R ₁ is an alkylene group having 1 to 24 carbon atoms or a substituted or unsubstituted arylene group having 6 to 18 carbon atoms, R ₂ is H and / or an alkyl group, z is an integer from 3 to 70, X ₁ is NH and / or O, R ₃ is an optionally substituted alkyl group having 1 to 30 carbon atoms which may be mono- or polyunsaturated, an optionally substituted aryl group having 6 to 18 carbon atoms, an optionally substituted cycloalkyl group having 4 to 10 carbon atoms, The free carboxyl group of the structural unit of formula IV may be in the form of an alkali metal, alkaline earth metal or ammonium salt. The method of claim 1, wherein in the structural unit of formula (I) to (IV), R is H, R ₁ is an alkylene group having 1 to 6 carbon atoms, R ₂ is H or CH ₃ , wherein the molar ratio of ethylene oxide units to propylene oxide units in the structural units of formula II and the structural units of formula III is from 0: 100 to 100: 0, R ₃ is an alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 carbon atoms, X ₁ is NH and / or O, A polymer mixture, characterized in that z is an integer from 5 to 60. The method of claim 1, wherein in the structural unit of formula (I) to (IV), R is H, R ₁ is an ethylene, propylene and / or isopropylene moiety, R ₂ is H or CH ₃ residue, wherein the molar ratio of ethylene oxide units to propylene oxide units is from 70:30 to 30:70, R ₃ is CH ₃ or C ₄ H ₉ residues, z is an integer from 25 to 50, A polymer mixture, characterized in that X ₁ is NH and / or O. 4. The ethylenically unsaturated monomer is a (methyl) acrylic acid derivative, preferably alkyl (meth) acrylate, aryl (meth) acrylate and maleic acid diester, preferably die At least one monomer selected from the group comprising alkyl maleateates. The polymer mixture according to any one of claims 1 to 4, characterized in that the weight ratio of comb copolymer (I) to copolymer (II) is in the range of 50:50 to 95: 5. The polymer according to any one of claims 1 to 5, characterized in that copolymer (II) can be obtained from optionally substituted styrene and maleic anhydride units by hydrolysis and chloride of anhydride groups. mixture. The polymer mixture according to claim 1, wherein the chloride of the free carboxyl group is generated by at least one compound having an amino group. The polymer mixture according to any one of claims 1 to 7, which can be obtained by mixing comb copolymer (I) with copolymer (II). Use of the polymer mixture according to any of claims 1 to 8 as wetting and dispersing agents. Use according to claim 9 for solids, preferably pigments and / or fillers. Use according to claim 9 or 10 for producing and / or treating solid concentrates, preferably pigment concentrates or pastes. Use according to any one of claims 9 to 11 for the manufacture and / or treatment of paints, printing inks, inkjet process inks, coatings, leather and / or textile dyes, ceramics, cosmetic preparations. 13. Use according to any of the claims 9 to 12, characterized in that conventional auxiliaries, preferably conventional binders, are also used. Paint or paste containing the polymer mixture according to any one of claims 1 to 8, at least one solid, preferably pigment, optionally an aqueous medium, optionally one or more binders, as wetting and dispersing agents. . A pigment whose surface has been modified with the polymer mixture according to any one of claims 1 to 8.